Aromatic sulfonhydrazides



Patented July 4,, 1950 AROMATIC SULFONHYDRAZIDES Joseph A. Sprung and Willy A. Schmidt, Easton;

Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 5, 1946,

Serial No. 714,146

1 Claim. (Cl. 26 -558) The present invention relates to El-aromatic sulfonhydrazides in which the terminal radical attached to the p-nitrogen atom is aromatic, said compounds being particularly useful in the production of azo dyestuils.

Many proposals have been made in the photographic art dealing with the preparation of dyestufl images. One of the classical methods involves the development of an exposed silver halide emulsion with a primary aromatic amino developer in the presence of a color former which reacts with the oxidation products of the developer to produce a dyestufl image in situ with the silver image formed in the development of the emulsion. The color formers generally employed contain either a phenolic hydroxyl group or a reactive methylene group and upon reaction with the oxidation products of a primary aromatic amino developer lead to dyestufls of the quinoneimine and azomethine class. These dyestufls leave something to be desired, particularly from the standpoint of their stability to light, acids, alkalies and the like.

It is known that the azo dyes are much more stable than theaforesaid dyes and proposals have been made to utilize the same in the formation of dyestufl images in photography. The method most generally employed is that known as the silver dye bleach-out method which involves the treatment of a diflusely dyed silver halide emulsion containing a silver image with a bleaching bath which destroys the dyestufl in cooperation with the silver image. This method, however, is disadvantageous from the standpoint of the fact that it cannot be used with taking film since the colored emulsion layers act as filters. The process is therefore generally confined to the production of colored prints where the exposure may be regulated at will. The art has accordingly been assiduously seeking a method which would enable the production of azo dyestufl images in photography while avoiding the objections inherent in the silver dye bleach-out method.

In our co-pending application Serial No. 5'74,- 810, filed January 26, 1945, now U. S. Patent 2,424,256, of which the present application is in part a continuation, we have disclosed the preparation of azo dvestufl images in color photography by developing an exposed silver halide emulsion with p-aromatic sulfonhydrazide in the presence of an azo dye coupling component. By this method there is produced in situ with the silver image an azo dyestufl image. The principle on which this process is based is discovery that p-aromatic sulfonhydrazides in the presence of a mild oxidizing agent such as that supplied by a latent silver image are converted into diazo sulfones which react with the usual azo dyestuff 1 components yielding azo dyes. It is pointed out in the prior application that the p-arpmatic sulionhydrazides which yield best results are those in which the aromatic radical linked to the p-nitrogen atom is substituted by a group more electropositive than hydrogen, such as an alkoxy, amino, or substituted amino group and the like. The diazo sulfones obtained from such sulfonhydrazides undergo coupling reactions similar to that 01' the corresponding diazonium salts. On the other hand, the aromatlc sulfonhydrazides which contain in the aryl ring attached to the p-nitrogen atom an electronegative substituent such as a nitro, carboxy, sulfo group or the like, yield on oxidation,

diazo sulfones which are quite reluctant to couple with azo dye components.

The p-sulionhydrazides in which the aromatic radical linked to the B-nitrogen atom is substituted by electropositive groups represent new compounds. Such compounds are not only very effective in the preparation oi. azo dye images as indicated above, but in addition may be employed to produce azo dyes in textile printing processes in general. The manner in which such compounds undergo conversion to azo dyes is illustrated by the following equations:

It is accordingly an object of the present invention to provide a new class of p-aromatic suli'onhydrazides in which the aromatic ring linked to the p-nitrogen atom is substituted by an electropositive group.

A further object of the present invention is paromatic sulfonhydrazides in which both terminal nuclei are aromatic and in which the aromatic ring linked to the fl-nitrogen atom is substituted by groups more electropositive than hydrogen.

A further object of the present invention is to produce a new class of fi-aromatic sulfonhydrazides which are especially suitable for the production of azo dyestuils.

Other and further important objects'of the invention will become apparent as the description proceeds.

the as The compounds contemplated by the present ,1 3 invention are typified by the -following general formulae:

R--aryl-NH NHSOz-R in which R is a substituent such as alkoxy, i. e., methoxy, ethoxy, butoxy, octadecoxy and the like, aryloxy such as phenoxy and the like, amino such as primary amino, alkylamino, i. e., methylamino, ethylamino, butylamino and the like, arylamino,

i. e., phenylamino, naphthylamino and the like, 1

aralkylamino, if e., benzylamino and the like, heterocyclic amino joined to the aryl ring either through a NH group on the heterocyclic radical or through the hetero nitrogen atom of the heterocyclic radical, i. e., morpholino, piperazino, 9-carbazolyl, etc., aliphatic acylamino, i. e., methane sulfonamido, ethyl sulfonamido, acetamido, propionamido and the like, aromatic acylamino, i. e., benzamido, benzene sulfonamido and the like; R represents acyclic and carbocyclic hydrocarbon ,radicals which may be aliphatic, alicycllc and aromatic. These hydrocarbon radicals may be substituted with groups-such as amino, acylamino, alkoxy, aryloxy, sulfo, carboxy, hydroxy, polyethenoxy,'w-sulfoalkoxy and the like; Z is a link- 0 2. p (2,5 diethoxy-4-benzamidophenyl) -benzenesulfonhydrazide M.CONHQNH NH SO 3. p (2,5 1 dimethoxy 4 benzamidophenyl) benzenesulfonhydrazide 4. p (2,5 diethoxy 4-benzamidophenyl) -pacetamidobenzenesulfonhydrazide O CIH5 NH-NH soQmz-c 0 CH;

\ CoHsCONH 5. B (8 benzenesulfonamide -1-naphthyl) -pacetamidobenzenesulfonhydrazide 6. p (4 ethoxyphenyl) benzenesulfonhydrazide CIHsOQ-NH-NH-SOQ '7. ,9 (2,5 diethoxy 4-benzamidophenyl) -4 aminobenzenesulfonhydrazide OCaHs 8. 5 (4 ethoxyphenyl) 4-(B'-sulfoethoxy)- benzenesulfonhydrazide (sodium salt) 9. p -(4-acetamidophenyl) -4-(fl'-sulfoethoxy) benzenesulfonhydrazlde (sodium salt) 0133c ONH-Q-NH-NH-BOz-Q-O clan-o m-soma 10. p (2,4 dimethyl -5-benzamidophenyl) -4- (5' sulfoethoxy) benzenesulfonhydrazide (sodium salt) NHCOCsHt CH3 NH-NH-SOz-QOCHz-ClI -SOaNii 11. ,8 (2,4 dimethyl-fi-benzamidophenyl)-4- acetamidobenzenesulfonhydrazide NHCOCQHB 12. p (3 phenylsulfonamido) 4-acetaminobenzenesulfonhydrazide mum-Q @NH-NH-SOQ-NH-C 0 cm 13. p (4 benzylaminophenyl) 4 aminobenzenesulfonhydrazide 14. p ('4 anilinophenyl) -4-aminobenzenesulfonhydrazide 15. p (4 N-morpholinophenyl) -4-aminobenzenesulfonhydrazide 16. ,8 (4 acetaminophenyl)-benzenesulfonhydrazide 17. p (3-ethylaminophenyl) -4- aminobenzenesulfonhydrazide NHNH-S OaQ-NH:

omooNn I NH-NHBOlCHIOHr-OCHICHiOH 39. p- (4-acetamidophenyl) -cyclohexanesulf onhydrazide 40. p-(4-ethoxyphenyl) 4 hydroxycyclohexanesulfonhydrazide Qnn-mr-sm-n Q a a HOB finic acids, on the other hand, are produced by:

reduction of the organic sulionyl chlorides.

The fl-arylsulfonhydrazides after oxidation to the diazo sulfones may be coupled with any of the usual azo dye coupling components such as aromatic compounds containing directing groups, i. e., phenolic hydroxy, alkoxy, amino and the like and possessing replaceable hydrogen atoms in the coupling position which is ortho or para to the directing group or with compounds possessing a reactive methylene group. Examples of such coupling components are:

Beta-naphthol N- (p-naphthyl) -3-hydroxy-2-naphthamide G salt H acid K acid Gamma acid 2-hydroxy-3-naphthoic acid anilide Acetoacetanilide l-phenyl-5-pyrazolone and the like By the choice of suitable components, it is, possible to secure azo dyes having a wide color range. Due to the greater inherent resonance of poly-azo dyestuffs and their resultant bluer color, we have found it desirable to use di-functional sulfonhydrazides to thereby obtain bis-azo dyes. It is also possible to prepare the poly-azo dyes by the reaction of di-iunctional sulfonhydrazides with coupling components containing one or more azo groups. this invention are also useful as components of pesticidal compositions, for example as insecticides.

The following examples, in which the parts-are by weight, further illustrate the invention:

Example l'.p-(2,5-dieth,oa:y-4 benzamidophenz l) -4-acetamidobenzenesulfonhydrazide The fl-aromatic sulfonhydrazides of a 8 A suspension oi 8.4 parts of 2,5-diethoxy-4- benzamidoaniline hydrochloride in 2.4 parts conc. hydrochloric acid, 9.8 parts formic acid and parts water was diazotized with a solution of ,1.8;parts sodium nitrite in 10 parts water. The

excess nitrous acid was destroyed with sultamlc acid and the filtered diazonium salt solution was added to a solution of 5.2 parts of p-acetamldobenzenesulflnic acid and 1.62 parts sodium carbonate monohydrate in 100 parts water. The orange colored precipitate was removed by filtration, washed well with water and air dried. The product weighing 11.3 parts (89%). melted with decomposition at approximately C.

A solution of 2.55 part of the above diazo-sulfone in a mixture of 50.0 parts of acetone, 0.75 part of glacial acetic acid'and 1.0 part of B20 is slowly treated at room temperature under vigorous stirring with zinc dust until the solution turns from a deep orange to a faint yellow color. The zine compounds are removed by filtration, and the cooled filtrate is diluted with 25.0 parts of water. The sulfonhydrazide, which separates, is removed by filtration and dried in a vacuum desiccator over phosphorus pentoxide. The yield is 1.6 parts or 62%. The material when recrystallized from dilute ethanol melted at 166 C. with decomposition.

Example II.p- (4-acetamidophenyl) -benzenesuljonhydrazide A suspension of 15.0 parts of p-aminoacetani lide in a solution of 10.7 parts of cone. hydrochloric acid, 36 parts of formic acid in parts of water was diazotized with a solution of 7.2

parts of sodium nitrite in 50 parts of water. The

excess nitrous acid was destroyed with sulfamic acid and the filtered diazonium salt solution was added to a solution of 17.2 parts of sodium benzenesulfinate in 50 parts of water. After 1 hour, the solid, 4-acetaminobenzene-diazo-(phenyl)- sulfone, was removed by filtration and washed with 500 parts of water. After the material was air-dried, 26.0 parts (86%) of the diazosulfone were obtained.

A solution of 15.2 parts of 4-acetamidobenzenediazo-(phenyl) -sulfone in 100 parts of dimethyl formamide, 6.1 parts of glacial acetic acid and 5 parts of water was slowly treated with zinc dust until the color of the solution had changed from a deep orange to a faint yellow. The temperature was not allowed to rise above 40 C. The zinc salts were removed by filtration and the filtrate was poured into a cold solution of 12 parts of cone. hydrochloric acid in 1000 parts of water. The sulfonhydrazide, which precipitated, was removed by filtration, washed well with water, and air dried. The yield is 11.4 parts or 75%.

Example III .p- (4-ethoaryphenyl) 4 (ff-sulfaethoxy) benzenesulfonhydrazide CiH, 'QNH-NH-SOGOCHz-CIh-SOJI A solution of 1.37 parts of p-phenetidine in 3.7 parts of formic acid and 10 parts of water is diazotized with a solution of 0.7 parts of sodium nitrite in 5 parts of water. The filtered diazonium salt solution is poured into a solution of 3.10 parts of the disodium salt of fl-(p-sulfinophenoxy)-ethanesu1fonic acid (prepared as in Example X hereof), in 10 parts of water. Fbrty anaaae parts of absolute ethanol was added and the precipitated diazosulfone is removed by filtration and washed with absolute ethanol and acetone. The yield of product, 4-ethoxybenzenedlazo-[4- (p'-sulfoethoxy)-phenyl] -sulfone, is 2.3 parts.

A solution of the, above compound in 15 parts of dlmethyl formamide and 1.1 parts of glacial acetic acid is treated with sufilcient zinc dust to cause the color of the solution to change from an orange to a faint yellow. The zinc salts are removed by filtration, and the filtrate is diluted with 80 parts of acetone. The sulfonhydrazide is removed by filtration and washed with acetone. After air drying, 0.9 part of product is obtained.

Example IV. p-(4-acetamidophenul)-4-(p'-suljoethvxy) -benzenesuljonhudrazide 011.0 ONE Nn-Nn-sor@- carom-some A suspension of 1.36 parts of p-aminoacetanllide in 3.7 parts of formic acid and 10 parts of water is diazotized with a solution of 0.69 part of sodium nitrite in parts of water. The excess nitrous acid is destroyed with sulfamic acid, and the filtered diazonium salt solution is poured into a solution of 3.10 parts of the di-sodium salt of -(p-su1finophenoxy) -ethanesulfonic acid (prepared as in Example X hereof) in 5 parts of water. Eighty parts of absolute ethanol are added, and the precipitated dlazosulfone'is removed by filtration and washed with absolute ethanol and acetone. The product, 4-acetamidobenzenediazo [4 (p sulfoethoxy) phenyllsulfone, amounts to 2.9 parts.

A solution of 1 part of the above compound in parts of dimethyl formamide and 1.1 parts glacial acetic acid is reduced with zinc dust in the usual manner. The zinc salts are removed by filtration, and the filtrate is diluted with 40 parts of acetone. The sulfonhydrazide, which is removed by filtration and air dried, amounts to 0.4 part.

Example V.p,pDi[4-p" sulfoethorcu) benzenesulfom l] 4,4 -dihydrazinodiphenylmethane NH-NH-SOQO cHrcm-soma A suspension of 1.98 parts of 4,4'-diaminodlphenylmethane in 3.7 parts of formic acid, 4.8 parts of cone. hydrochloric acid and 10 parts of water is tetrazotized with a solution of 1.40 parts of sodium nitrite in 5 parts of water. The filtered diazonium salt solution is poured into a solution of 6.2 parts of the di-sodium salt of p-(p-sulfinophenoxy) -ethanesulfonic acid in 10 parts of water. Eighty parts of absolute ethanol are added, and the precipitated diazosulfone is removed by filtration and washed with absolute ethanol and acetone and dried. The product, 4,4'-diphenylmethane bis diazo [4 (13' sulfoethoxy) -phenyl]-disulfone, amounts to 7.0 parts.

A solution of 1.99 parts of the diazosulfone in 25 parts of dimethyl formamide and 1.2 parts of glacial acetic acid is reduced with zinc dust in the usual manner. The zinc salts are removed by filtration and the filtrate diluted with 80 parts of acetone. The sulfonhydrazide is removed by filtration and washed with acetone. After drying, 1.3 parts of the product are obtained.

QNrI-NH-sOQ-O CHrCHs-BOiNS Example VI.-p,p' Di(4 acetamidobenzenesullonul) 4,4'-dihudrazmodiphenulmethane NH-NH-SO A solution of 3.96 parts of 4,4-diaminodlphenylmethane in 7.3 parts of formic acid, 9.6

parts of cone. hydrochloric acid and 50 parts of water is tetrazotized with an aqueous solution containing 2.8 parts of sodium nitrite. The excess nitrous acid is destroyed with sulfamic acid and the filtered diazonium salt solution is poured into a solution of 8.4 parts of p-acetamidobenzenesulfinlc. acid and 2.7 parts of sodium carbonate monohydrate in 50 parts oi. water. The diazosulfone is removed by filtration, washed well with water and air dried. The product, 4,4'-diphenylmethane bis diazo (4 acetamidophenyl)-disulfone, amounts to 10.5 parts.

A solution of the above diazosulfone in 50 partsof dimethyl formamide and 5.3 parts of glacial acetic acid is reduced in the usual manner with zinc dust. The zinc salts are removed by filtration and the filtrate poured into water. The sulfonhydrazide is removed by filtration and washed well with water. After air drying, the product amounts to 8.2 parts.

Example VII.p-(z-methoiwnaphthul) 4-acetamlnobenzenesulfonhydrazide O CH:

Example VIIL-pLp' Di (4 acetamidobenzenesulfonyl) 3,3 dimethoxy 4,4'-biphen11lenedihydrazine OCH:

A solution of 3.17 parts of dianisidine dihydrochloride in 6 parts of formic acid and 25 parts of water was tetrazotized with a solution of 1.44 parts of sodium nitrite in 10 parts of water. The excess nitrous acid was. destroyed with sulfamic acid and the filtered diazonium salt solution was poured into a solution of 4.0 parts of p-acetamldoben'zenesulfinic' acid and 1.24 parts of sodium carbonate monohydrate in 25 parts of water. The diazosulfone was removed by filtration, washed well with water and dried in a vacuum desiccator over phosphorus pentoxide. The yield amounts to 5.4 parts (81%) of 3,3-di- NIH-O 0 OH:

methoxy 4,4 biphenyl bis diazo (4 acetohenyl) -disulfone. I

x solfition of 5.0 parts of 3,3-dimethoxy-4,4'- biphenyl bis diazo (4 acetamidophenyD- disulfone in 35 parts of dimethyl formamide and 2.1 parts of glacial acetic acid was reduced in the usual manner with zinc dust. The zinc salts were removed by filtration and the filtrate was poured into 100 parts of water. The sulfonhydrazide was removed by filtration, washed well with water and dried in avacuum desiccator over phosphorus pentoxide. The yield is 4.1 parts Example IX.-p-(2-ethoxyphenyl) -methane suljonhydrazide Qmn-NH-smcm CzHl A mixture of 37.0 parts of 2-ethoxyphenylhydrazine hydrochloride, 22.9 parts of methane sulfonyl chloride and 33.6 parts of sodium bicarbonate in 283 parts of ethyl ether was stirred for 1 hour at room temperature and finally refiuxed for 2 hours on a steam bath. The cooled mixture was treated with 264 parts of low-boiling petroleum ether and the precipitated material was removed by filtration and washed with petroleum ether. The solid was digested twice at room temperature with dilute hydrochloric acid (6 parts of hydrochloric acid in 250 parts of water) and finally washed with water and air dried. The product, melting at 105 C., amounted to 40 parts (87%).

Analysis: Calc. for C9H1403N2S, C=46.94; H=6.12. Found, C=47.12; H=6.02,

Example X.,8,,B-Di[4-(p" sulfoethomy) benzenesulfonyl] 3,3 dimethoxy 4,4 biphenylene dihydra'zine A solution of 100.5 parts of p-phenoxyethyl bromide (prepared by the method, of Organic Syntheses, Coll. vol. I (2nd ed.), p. 436, note 6) in 500 parts of chloroform was cooled to C. (ice salt bath) and treated with 250 parts chlorosulfonic acid at such a rate that the temperature was not allowed to rise above C. The addition of the first mole of chlorosulfonic acid was accompanied by a rapid rise in temperature and a copious evolution of hydrogen chloride. Although the remainder of the chlorosulfonic acid was added very rapidly, no appreciable rise in temperature was noted. The reaction mixture was poured into ice water and the chloroform layer was separated. The aqueous layer was extracted once with 50 parts of chloroform and the combined chloroform extract was washed once with 250 parts of cold water. After the chloroform solution had been dried over anhydrous sodium sulfate, the chloroform was removed by distillation (steam bath), and the-liquid residue was digested with 240 parts of cold low-boiling petroleum ether. The solid was removed by filtration and dried in a vacuum desiccator over sodium hydroxide. The compound, 4-(fi-bromethoxy)-benzenesulfonyl chloride, amounted to 124 parts (82% yield) and melted at 65 C.

To a well-stirred suspension of 120.0 parts of finely powdered 4-(fi-bromethoxy)-benzenesulfonyl chloride and 63.0 parts of anhydrous sodium OCH;

sulfite in 1000 parts of water, there was added sodium hydroxide solution at such a rate that tion remained constant. The cooled, filtered solution was acidified with 83 parts of cone. hydrochloric acid, and the precipitated material was removed by filtration. The crude sulfinic acid 1 was redissolved in 250 parts of 10% sodium carv and dried on a porous plate.

bonate solution and 1000 parts of water and was reprecipitated with 60 parts of cone. hydrochloric acid. The, solid material wasremoved by filtration, washed with a small amount of cold water The compound, 4-(p-bromethoxy) -benzenesulfinic acid, amounted to 75 parts (71% yield) and melted between 80 and 90 C., depending on the rate of heating.

Sixty-six parts of 4-(fl-bromethoxy)-benzenesulfinic acid were added to a solution of 16.0 parts of sodium carbonate monohydrate in 250 parts of water. When carbon dioxide was no longer evolved, 33.0 parts of anhydrous sodium sulflte were added and the whole was refluxed for 1.5 hours. The solution was concentrated to about half its volum and then treated with 320 parts of absolute ethanol. After the mixture had been allowed to remain in an ice bath for 1 hour,

the product which separated was removed by filtration. The filter cake was washed once with a cold solution of 15 parts of water in parts of absolute ethanol. The disodium salt of [Si-(4- sulfinophenoxy) -ethane sulfonic acid, after'drying in an oven at 105 C., amounted to 64.0 parts (83% yield).

A warm solution of 3.1? parts of pure dianisidine dihydrochloride in 2.4 parts of formic acid and 15 parts of water was cooled to 5 C. and

OCH;

, azonium salt solution was poured into a solution of 6.5 parts of the the di-sodium salt of 18-(4- sulfinophenoxy) -ethanesulfonic acid in 10.0 parts of water. Eighty parts of absolute ethanol were added and the material, which separated, was removed by filtration. The compound, 3,3'-dimethoxy-4,4' biphenylene bis diazo- [4-(p"- sulfoethoxy)-phenyll-sulfone was digested with parts of acetone and air dried. The yield is 6.8 parts (81%). v

A solution of 2.1 parts of the above diazosulfone in 2.0 parts of water, 1.0 part of acetic acid and 25.0 parts of dimethylformamide was treated with zinc dust at room temperature until the color of the solution changed from a deep red to a faint orange. The zinc compounds were removed by filtration, and the filtrate was poured into parts of cold acetone. The precipitate, fi, 3-di[4-' (,9" sulfoethoxy) benzenesulfonyl] 3,3 dimethoxy-4,4'-bi-phenylene dihydrazine, was removed by filtration and washed with acetone. The yield is 1.3 parts( 62% Various modifications of the invention will occur to persons skilled in the art and we therefore do not intend to be limited in the patent granted except as necessitated by the prior art and the appended claims.

13 14 We claim: FOREIGN PATENTS A fl-aromatic smtonhydrazide o! the following Number- Country Date 68,719 Germany Apr. 26, 1893 70,459 Germany Aug. 30, 1893 12,872 Great Britain 1900 OTHER. REFERENCES JbsEPH A. SPRUNG. 155121115334. Ber. Deut. Chem., vol. (1877), pp. Llmpricht, "Ber. Deut. Chem.," v01. (1887). REFERENCES crrm 1239-1241- Altschu], Ber. Deut. Chem., vol. (1892), pp. The following references are of record In th 1843 1844 me this P Hantsch et 9.1., Ber. Deut. Chem., v01.

UNITED STATES PATENTS 15 9 .pp-31 -31 Number Name Date Gatterman, Ber. Deut. Chem," vol. 32 (1899),

12.1154. 2,272,134 Shappirio Feb. 3, 1942 u n 24,256 schmmeul 13722.19 3:1], J. Chem. Soc. (London), 1936, pp. 1242 so Saunders The Aromatic Dlazo Compounds and Their Technical Applications" (1936) pp. 48 to 50. 

